CN103949653B - A kind of product separation of supercritical water thermal synthesis system and organic ligand recovery system - Google Patents
A kind of product separation of supercritical water thermal synthesis system and organic ligand recovery system Download PDFInfo
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- CN103949653B CN103949653B CN201410131206.8A CN201410131206A CN103949653B CN 103949653 B CN103949653 B CN 103949653B CN 201410131206 A CN201410131206 A CN 201410131206A CN 103949653 B CN103949653 B CN 103949653B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of product separation and organic ligand recovery system of supercritical water thermal synthesis system, comprise the first centrifuge, the second centrifuge, the 3rd centrifuge, service sink, anti-oxidant treatment pond, antioxidant storage tank, vacuum drier, oil water separator, reverse osmosis units and biochemical treatment unit; Wherein, the filter residue flowed out from the 3rd centrifuge can obtain nano level metal or metal oxide particle after vacuum drier vacuum drying; Filtered by oil water separator coarse filtration and reverse osmosis units essence, organic ligand high efficiente callback can be realized; Water outlet through biochemical treatment unit can qualified discharge.The present invention can realize the nano level metal of abundant separation and purification or metal oxide particle, and recycles the organic ligand in product, promotes feasibility and the economy of supercritical water thermal synthesis technology.Meanwhile, the present invention increases biochemical treatment unit, ensures standard water discharge, and system non-secondary pollution discharges.
Description
[technical field]
The present invention relates to the supercritical water thermal synthesis field of nano metal or metal oxide nano particles, particularly a kind of product separation of supercritical water thermal synthesis system and organic ligand recovery system.
[background technology]
Nano particle, refers to the microscopic particles of nanometer scale.It is defined as the particle being at least less than 100 nanometers in a dimension.And nano metal or metal oxide nano particles, because it has great specific area and unique electricity, calorifics, magnetics, optics and mechanical property, be widely used in the fields such as catalyst, sensor, battery, glass and pottery.
Supercritical water thermal synthesis is a kind of completely new approach preparing nano metal or metal oxide nano particles.So-called overcritical hydrothermal synthesis reaction refers in airtight high-temperature high-voltage reaction device, with supercritical water (T >=374.15 DEG C, P >=22.12MPa) as reaction medium, make predecessor that hydrolysis and dehydration generation metal oxide occur, and then nucleation, growth, final form the nano-metal-oxide crystal grain with certain particle size and crystal habit.Under reducing agent existence condition, predecessor is hydrolyzed, dewater and reduction reaction, generates nano metal crystal grain.The principle of overcritical hydrothermal synthesis reaction is as follows: slaine ML
xfirst with water power from the OH gone out
-there is hydrolysis and generate metal hydroxides M (OH)
x, and then there is dehydration again and generate metal oxide MO
x/2, reducing agent is (as H
2) metal oxide MO when existing
x/2there is reduction reaction and generate metal M.Course of reaction is such as formula shown in (1) ~ (3):
Hydrolysis ML
x+ xOH
-→ M (OH)
x+ xL
-(1)
Dehydration M (OH)
x→ MO
x/2+ x/2H
2o (2)
H
2reduction reaction MO when existing
x/2+ x/2H
2→ M+x/2H
2o (3)
Predecessor used in reaction is the mixture of metal salt solution and alkali lye or the mixture of metal salt solution and alkali lye, reducing agent and organic ligand.Reducing agent used is hydrogen or formic acid etc., obtains nano-metal particle for carrying out reduction to the metal ion of high-valence state.Organic ligand used has good heat endurance in supercritical water, contains carboxyl or amido isopolarity functional group in molecule simultaneously, for preventing the generation of particle agglomeration phenomenon, improves the dispersiveness of nano particle.
The advantages such as supercritical water thermal synthesis technology prepares nano metal or metal oxide nano particles has environmental protection, particle purity is high, granularity is little, favorable dispersibility.Wherein, the separation of nano-particle product and the recycling of organic ligand are of great significance for the economy tool promoting Hydrothermal Synthesis technology.
[summary of the invention]
The object of this invention is to provide a kind of product separation and organic ligand recovery system of supercritical water thermal synthesis system, the method can the fully nano level metal of abstraction and purification or metal oxide particle, and the organic ligand recycled in product, promote feasibility and the economy of supercritical water thermal synthesis technology, simultaneously, increase biochemical treatment unit, ensure standard water discharge, system non-secondary pollution.
For achieving the above object, the present invention is achieved by the following technical solutions:
The product separation of supercritical water thermal synthesis system and an organic ligand recovery system, comprise the first centrifuge, the second centrifuge, the 3rd centrifuge, service sink, anti-oxidant treatment pond, vacuum drier, oil water separator, reverse osmosis units and biochemical treatment unit; Wherein,
The outlet of supercritical water thermal synthesis system connects the entrance of the first centrifuge, and the filtrate (liquid of the first centrifuge connects the entrance of oil water separator, and the sludge outlet of the first centrifuge connects the entrance of service sink;
The side of service sink is provided with absolute ethyl alcohol entrance, the outlet of service sink connects the entrance of the second centrifuge, the filtrate (liquid of the second centrifuge connects the first entrance of supercritical water thermal synthesis system, the sludge outlet of the second centrifuge connects the upper entrance in anti-oxidant treatment pond, the outlet in anti-oxidant treatment pond connects the entrance of the 3rd centrifuge, and the sludge outlet of the 3rd centrifuge connects the entrance of vacuum drier;
The oil phase outlet of oil water separator connects the second entrance of supercritical water thermal synthesis system, the aqueous phase outlet of oil water separator connects the entrance of reverse osmosis units, the dense water out of reverse osmosis units is connected with the entrance of oil water separator after merging with the filtrate (liquid of the first centrifuge again, and the water outlet of reverse osmosis units connects the entrance of biochemical treatment unit.
The present invention improves further and is, also comprises antioxidant storage tank, and wherein, the filtrate (liquid of the 3rd centrifuge connects the entrance of antioxidant storage tank, and the outlet of antioxidant storage tank connects the side inlet in anti-oxidant treatment pond.
The present invention improves further and is, the antioxidant in antioxidant storage tank (6) is ethanol and 5 ~ 10% stearic mixtures of 90 ~ 95%.
Compared with prior art, advantage of the present invention is:
1, the present invention is combined with supercritical water thermal synthesis reaction system, carries out centrifugation, ethanol purge, anti-oxidant treatment and vacuum drying to product, effectively can obtain highly purified nano level metal or metal oxide particle, improves the price of product; Simultaneously by water-oil separating and reverse osmosis units, effectively can utilize and reclaim unreacted organic ligand, reduce the operating cost of system.
2, present system non-secondary pollution, its water outlet at reverse osmosis units increases biochemical treatment unit, ensures standard water discharge; Ethanol waste liquid after cleaning can be used as fuel and enters Hydrothermal Synthesis system and provide heat; Further, antioxidant used can Reusability.
[accompanying drawing explanation]
Fig. 1 is process flow diagram of the present invention.
In figure: 1 is the first centrifuge; 2 is the second centrifuge; 3 is the 3rd centrifuge; 4 is service sink; 5 is anti-oxidant treatment pond; 6 is antioxidant storage tank; 7 is vacuum drier; 8 is oil water separator; 9 is reverse osmosis units; 10 is biochemical processing unit; 11 is the product of supercritical water thermal synthesis system; 12 is organic ligand; 13 is ethanol waste liquid; 14 is dense water; 15 is fresh water.
[detailed description of the invention]
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
See Fig. 1, the product separation of a kind of supercritical water thermal synthesis of the present invention system and organic ligand recovery system, comprise the first centrifuge 1, second centrifuge 2, the 3rd centrifuge 3, service sink 4, anti-oxidant treatment pond 5, antioxidant storage tank 6, vacuum drier 7, oil water separator 8, reverse osmosis units 9 and biochemical treatment unit 10.
Wherein, the outlet of supercritical water thermal synthesis system connects the entrance of the first centrifuge 1, and the filtrate (liquid of the first centrifuge 1 connects the entrance of oil water separator 8, and the sludge outlet of the first centrifuge 1 connects the entrance of service sink 4;
The side of service sink 4 is provided with absolute ethyl alcohol entrance, the outlet of service sink 4 connects the entrance of the second centrifuge 2, the filtrate (liquid of the second centrifuge 2 connects the first entrance of supercritical water thermal synthesis system, the sludge outlet of the second centrifuge 2 connects the upper entrance in anti-oxidant treatment pond 5, the outlet in anti-oxidant treatment pond 5 connects the entrance of the 3rd centrifuge 3, the filtrate (liquid of the 3rd centrifuge 3 connects the entrance of antioxidant storage tank 6, the outlet of antioxidant storage tank 6 connects the side inlet in anti-oxidant treatment pond 5, the sludge outlet of the 3rd centrifuge 3 connects the entrance of vacuum drier 7, nano level metal or metal oxide particle can be obtained after vacuum drier 7 vacuum drying.
The oil phase outlet of oil water separator 8 connects the second entrance of supercritical water thermal synthesis system, the aqueous phase outlet of oil water separator 8 connects the entrance of reverse osmosis units 9, filter 9 by the coarse filtration of above-mentioned oil water separator 8 and reverse osmosis units essence, organic ligand high efficiente callback can be realized; Be connected with the entrance of oil water separator 8 after the dense water out of reverse osmosis units 9 merges with the filtrate (liquid of the first centrifuge 1, the water outlet of reverse osmosis units 9 connects the entrance of biochemical treatment unit 10, and the water outlet through biochemical treatment unit 10 can qualified discharge again.
The present embodiment prepares Nanometer Copper for supercritical water thermal synthesis, is described Nanometer Copper separation and organic ligand recovery system:
The product 11 of supercritical water thermal synthesis system enters the first centrifuge 1 and carries out centrifugation, and the filtrate (liquid of the first centrifuge 1 connects the entrance of oil water separator 8, and the sludge outlet of the first centrifuge 1 connects the entrance of service sink 4.
The outlet of service sink 4 connects the entrance of the second centrifuge 2, and the filtrate of the second centrifuge 2 is the ethanol waste liquid 13 containing organic impurities, and its fuel that can be used as enters supercritical water thermal synthesis system and provides institute's calorific requirement; The sludge outlet of the second centrifuge 2 connects the upper entrance in anti-oxidant treatment pond 5.
The outlet of antioxidant storage tank 6 is connected with the side inlet in anti-oxidant treatment pond 5, the outlet in anti-oxidant treatment pond 5 is connected with the entrance of the 3rd centrifuge 3, the filtrate (liquid of the 3rd centrifuge 3 connects the entrance of antioxidant storage tank 6, and the sludge outlet of the 3rd centrifuge 3 connects the entrance of vacuum drier 7.Nanometer Copper product can be obtained after vacuum drier 7 vacuum drying treatment.
The aqueous phase outlet of oil water separator 8 is connected with the entrance of reverse osmosis units 9, the oil phase outlet of oil water separator 8 connects the second entrance of supercritical water thermal synthesis system, this oil phase is unreacted organic ligand 12, the recycling of supercritical water thermal synthesis system can be entered, dense water 14 is through the entrance of the dense water out inflow oil water separator 8 of reverse osmosis units 9, fresh water 15 flows into the entrance of biochemical unit 10 through the water outlet of reverse osmosis units 9, and the water after biochemical treatment can qualified discharge.
In order to understand further the present invention, now an explanation is done to the technological principle of above-described embodiment.
1) pre-reaction material of supercritical water thermal synthesis is the mixture of copper salt solution and alkali lye, reducing agent and organic ligand, comprises water, Nanometer Copper, unreacted organic ligand, bivalent cupric ion and a small amount of reducing agent and decompose the organic molecule product (as formic acid etc.) produced in the product 11 of supercritical water thermal synthesis.Being separated pure nano copper particle needs through the link such as centrifugal, cleaning, anti-oxidant treatment, drying; The separation and recovery of organic ligand needs through the link such as centrifugal, water-oil separating, UF membrane.
2) Nanometer Copper and a small amount of organic matter such as organic ligand, formic acid is comprised in the filter residue of the first centrifuge 1.Absolute ethyl alcohol is added as cleaning agent, for cleaning the impurity organic matter comprised in Nanometer Copper at service sink 4.
3) for preventing Nanometer Copper generation oxidation reaction, need to carry out anti-oxidant treatment to Nanometer Copper in anti-oxidant pond 5, antioxidant used is ethanol and 5 ~ 10% stearic mixtures of 90 ~ 95%.
Claims (2)
1. the product separation of a supercritical water thermal synthesis system and organic ligand recovery system, it is characterized in that, comprise the first centrifuge (1), the second centrifuge (2), the 3rd centrifuge (3), service sink (4), anti-oxidant treatment pond (5), vacuum drier (7), oil water separator (8), reverse osmosis units (9) and biochemical treatment unit (10); Wherein,
The outlet of supercritical water thermal synthesis system connects the entrance of the first centrifuge (1), the filtrate (liquid of the first centrifuge (1) connects the entrance of oil water separator (8), and the sludge outlet of the first centrifuge (1) connects the entrance of service sink (4);
The side of service sink (4) is provided with absolute ethyl alcohol entrance, the outlet of service sink (4) connects the entrance of the second centrifuge (2), the filtrate (liquid of the second centrifuge (2) connects the first entrance of supercritical water thermal synthesis system, the sludge outlet of the second centrifuge (2) connects the upper entrance in anti-oxidant treatment pond (5), the outlet in anti-oxidant treatment pond (5) connects the entrance of the 3rd centrifuge (3), and the sludge outlet of the 3rd centrifuge (3) connects the entrance of vacuum drier (7);
The oil phase outlet of oil water separator (8) connects the second entrance of supercritical water thermal synthesis system, the aqueous phase outlet of oil water separator (8) connects the entrance of reverse osmosis units (9), be connected with the entrance of oil water separator (8) after the dense water out of reverse osmosis units (9) merges with the filtrate (liquid of the first centrifuge (1), the water outlet of reverse osmosis units (9) connects the entrance of biochemical treatment unit (10) again.
2. the product separation of a kind of supercritical water thermal synthesis system according to claim 1 and organic ligand recovery system, it is characterized in that, also comprise antioxidant storage tank (6), wherein, the filtrate (liquid of the 3rd centrifuge (3) connects the entrance of antioxidant storage tank (6), and the outlet of antioxidant storage tank (6) connects the side inlet in anti-oxidant treatment pond (5).
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| CN104772470B (en) * | 2015-03-26 | 2017-03-01 | 太原理工大学 | The method that xenogenesis nucleus nano metal powder is prepared in closely/supercritical water thermal reduction |
| CN110942916A (en) * | 2018-09-21 | 2020-03-31 | 钰冠科技股份有限公司 | Purification system for soluble nanoparticles |
| CN112091230A (en) * | 2019-06-18 | 2020-12-18 | 上海沪正实业有限公司 | Nano copper particles and preparation method thereof |
| CN111099780B (en) * | 2019-12-30 | 2021-05-14 | 西安交通大学 | Energy comprehensive utilization supercritical hydrothermal synthesis system and method for nanoparticles |
| CN111774580B (en) * | 2020-07-01 | 2021-07-27 | 西安交通大学 | Continuous post-treatment system and method for preparing nano material by supercritical hydrothermal synthesis |
| CN115536057B (en) * | 2022-10-11 | 2023-11-24 | 广西华锡集团股份有限公司 | Method for preparing nano metal oxide by using near supercritical fluid and production equipment |
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